CN115020882B - Nano injection molding technology and top cover structure - Google Patents
Nano injection molding technology and top cover structure Download PDFInfo
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- CN115020882B CN115020882B CN202210660081.2A CN202210660081A CN115020882B CN 115020882 B CN115020882 B CN 115020882B CN 202210660081 A CN202210660081 A CN 202210660081A CN 115020882 B CN115020882 B CN 115020882B
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- 238000001746 injection moulding Methods 0.000 title claims abstract description 48
- 238000005516 engineering process Methods 0.000 title claims abstract description 17
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 60
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000007709 nanocrystallization Methods 0.000 claims abstract description 28
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 20
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 20
- 239000000243 solution Substances 0.000 claims abstract description 13
- 238000006056 electrooxidation reaction Methods 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims description 34
- 229910052782 aluminium Inorganic materials 0.000 claims description 33
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 33
- 238000005406 washing Methods 0.000 claims description 22
- 230000007797 corrosion Effects 0.000 claims description 21
- 238000005260 corrosion Methods 0.000 claims description 21
- 239000003112 inhibitor Substances 0.000 claims description 14
- 239000012778 molding material Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- JRBRVDCKNXZZGH-UHFFFAOYSA-N alumane;copper Chemical group [AlH3].[Cu] JRBRVDCKNXZZGH-UHFFFAOYSA-N 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 2
- ZDYUUBIMAGBMPY-UHFFFAOYSA-N oxalic acid;hydrate Chemical compound O.OC(=O)C(O)=O ZDYUUBIMAGBMPY-UHFFFAOYSA-N 0.000 claims description 2
- 238000005554 pickling Methods 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 238000005868 electrolysis reaction Methods 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 23
- 238000007789 sealing Methods 0.000 description 15
- 239000000463 material Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000012512 characterization method Methods 0.000 description 6
- 238000003466 welding Methods 0.000 description 6
- 239000011148 porous material Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002070 nanowire Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
- H01M50/147—Lids or covers
- H01M50/148—Lids or covers characterised by their shape
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/17—Component parts, details or accessories; Auxiliary operations
- B29C45/76—Measuring, controlling or regulating
- B29C45/77—Measuring, controlling or regulating of velocity or pressure of moulding material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/17—Component parts, details or accessories; Auxiliary operations
- B29C45/76—Measuring, controlling or regulating
- B29C45/78—Measuring, controlling or regulating of temperature
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
- H01M50/147—Lids or covers
- H01M50/155—Lids or covers characterised by the material
- H01M50/157—Inorganic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
- H01M50/183—Sealing members
- H01M50/186—Sealing members characterised by the disposition of the sealing members
- H01M50/188—Sealing members characterised by the disposition of the sealing members the sealing members being arranged between the lid and terminal
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
- H01M50/183—Sealing members
- H01M50/19—Sealing members characterised by the material
- H01M50/193—Organic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/543—Terminals
- H01M50/547—Terminals characterised by the disposition of the terminals on the cells
- H01M50/55—Terminals characterised by the disposition of the terminals on the cells on the same side of the cell
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/543—Terminals
- H01M50/552—Terminals characterised by their shape
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/543—Terminals
- H01M50/564—Terminals characterised by their manufacturing process
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2945/00—Indexing scheme relating to injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould
- B29C2945/76—Measuring, controlling or regulating
- B29C2945/76494—Controlled parameter
- B29C2945/76498—Pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2945/00—Indexing scheme relating to injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould
- B29C2945/76—Measuring, controlling or regulating
- B29C2945/76494—Controlled parameter
- B29C2945/76531—Temperature
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The application relates to the field of battery covers, in particular to a nano injection molding technology and a top cover structure. The top cover structure comprises a top cover, an anode column and a cathode column, wherein the top cover is respectively provided with an anode region and a cathode region, and the anode column and the cathode region are connected through a nano injection molding technology. The nano injection molding technology comprises the following steps: pretreatment is carried out firstly; then the positive and negative electrode areas and the positive and negative electrode columns of the top cover are subjected to nanocrystallization; and finally, filling gaps at the joints of the positive electrode and the negative electrode columns and the positive electrode and the negative electrode regions respectively through an injection molding process. The Chi Huanshi agent is prepared by mixing oxalic acid and phosphoric acid water solution, and has anode current carrying density of 0.5-5mA/m at 25-35deg.C 2 The voltage of the feed back stabilized voltage source is 20-30V, and the nanocrystallization treatment is carried out under the conditions of electrolysis and electrochemical corrosion time of 2-15min. The top cover structure prepared by the application improves the connection stability and the tightness between the top cover and the pole of the battery, thereby improving the safety performance of the battery.
Description
Technical Field
The application relates to the field of battery covers, in particular to a nano injection molding technology and a top cover structure.
Background
With the popularization of new energy, power batteries are widely applied to vehicles such as electric automobiles, electric bicycles, electric trains and the like, so that the use safety of the batteries is a concern of people.
The current power battery is mainly characterized in that the current is conducted inside and outside through a pole, the pole is connected with a battery top cover, one end of the pole is connected with an external circuit of the power battery, and the other end of the pole stretches into the battery to be connected with a battery core in the battery, so that the charge and discharge functions of the battery are realized, and the voltage resistance and the tightness of the power battery are required to be higher. The sealing ring is used for sealing between the current battery top cover and the pole to improve the sealing property between the battery top cover and the pole, thereby improving the safety of the battery. However, the sealing ring may fall off due to aging or improper installation during use, so that the power battery has a leakage risk, which results in scrapping of the battery and creates a safety problem, and thus improvement is required to improve the connection stability and tightness between the battery top cover and the pole.
Disclosure of Invention
In order to improve the connection stability and the tightness between the battery top cover and the pole, thereby improving the safety performance of the battery, the application provides a nano injection molding technology and a top cover structure.
The application provides a top cover structure, which comprises a top cover, an anode column and a cathode column, wherein the top cover is respectively provided with an anode region and a cathode region, the anode column and the cathode column are connected with the anode region and the cathode region through a nano injection molding technology, and the nano injection molding technology comprises the following steps:
s1, pretreatment: the top cover, the positive pole and the negative pole are firstly subjected to heat treatment, and then are subjected to alkali washing and acid washing;
s2, nanocrystallization treatment of positive and negative electrode areas of the top cover: positioning by taking a top cover as an anode and a carbon rod as a cathode and taking an anode region and a cathode region as centers, and directionally corroding the anode region and the cathode region in the corrosion inhibitor of the electrolytic cell;
s3, nanocrystallization treatment of positive and negative electrode columns: respectively taking the positive and negative poles as anodes and taking a carbon rod as a cathode, and directionally corroding the parts of the positive and negative poles, which are connected with the positive and negative pole areas, in the corrosion inhibitor of the electrolytic cell;
s4, filling gaps at the joints of the positive electrode column and the negative electrode column and the positive electrode region and the negative electrode region respectively through an injection molding process;
the electrolyte Chi Huanshi agent is formed by mixing an oxalic acid aqueous solution and a phosphoric acid aqueous solution, wherein the mass concentration of the oxalic acid aqueous solution is 8-10g/L, the mass concentration of the phosphoric acid aqueous solution is 10-50g/L, and the volume ratio of the oxalic acid aqueous solution to the phosphoric acid aqueous solution is (5-6): 100.
In step S2 and step S3, the conditions of the nanocrystallization process are: the temperature is 25-35 ℃, and the current carrying density of the anode is 0.5-5mA/m 2 The voltage of the feed back stabilized voltage source is 20-30V, and the electrolytic electrochemical corrosion time is 2-15min.
By adopting the technical scheme, the mixed solution of oxalic acid aqueous solution and phosphoric acid aqueous solution is used as the electrolytic cell corrosion inhibitor, and under the nanocrystallization treatment condition, the positive and negative electrode areas and the positive and negative electrode columns of the top cover are subjected to directional corrosion, so that the positive and negative electrode areas and the connecting parts of the positive and negative electrode columns and the positive and negative electrode areas form porous Anodic Aluminum Oxide (AAO), the AAO has a honeycomb-shaped hole structure which is accurate, unchanged, uniform in pore diameter, adjustable in pore size and height, and the holes are not crossed and communicated on the side surfaces. After the AAO is formed, gaps at the joints of the positive electrode column and the negative electrode column and the positive electrode region and the negative electrode region are filled by adopting an injection molding process, and injection molding materials serve as nano anchor nails to be respectively connected with AAO honeycomb holes on the positive electrode column and the negative electrode column and the positive electrode region and the negative electrode region, so that the positive electrode column and the negative electrode column are tightly connected with the top cover to replace the original sealing rings, the positive electrode column and the negative electrode column are integrally connected with the top cover, the connection stability and the sealing performance between the top cover and the electrode column of the battery are improved, and the safety performance of the battery is further improved. While AAO is generally used as a template for preparing nanowires by electrodeposition, preparing a nano lattice by sputtering or MEB, preparing a nano structure by sol-gel, and the like, the application applies the acid corrosion inhibitor primary cell principle micro corrosion combined with anodic oxidation directional corrosion nanocrystallization treatment technology to the field of cell covers, and the integrated injection molding realizes the tight connection of positive and negative pole columns and a top cover, so that the tightness between the positive and negative pole columns can be improved, and the large-scale production can be performed, thereby reducing the cost.
Optionally, in step S1, the conditions of the heat treatment are: placing the top cover and the positive and negative electrode columns in an environment with the temperature rising rate of 5 ℃/min to 450-500 ℃, and standing for 1.5-2.5h.
Optionally, in step S1, the alkaline washing conditions are: washing the heat treated top cover and the positive and negative poles with sodium hydroxide solution of molar concentration 1mol/L at 25-30deg.C for 2-8min.
Optionally, in step S1, the conditions for pickling are: washing the top cover and the anode and cathode columns after alkali washing with oxalic acid water solution with the mass concentration of 20g/L for 2-5min at room temperature.
By using the heat treatment method, the stress and internal lattice defects of the top cover and the anode and cathode column materials can be removed, and meanwhile, the pollutants on the surfaces can be removed. After the acid washing and alkali washing method is used for treatment, grease and an oxidation film on the surface can be removed, so that the surface is smoother, the influence of the appearance of the surface on the formation of AAO is reduced, the AAO is in more sufficient contact with an electrolytic cell solution, a more uniform and compact AAO structure is formed, and the subsequent injection molding is more facilitated.
Optionally, the top cover is 3 series aluminum; the positive pole is 1 series aluminum or 3 series aluminum; the negative pole post is copper aluminum composite structure, copper is T2 copper in the copper aluminum composite structure, and aluminum is 1 series aluminum or 3 series aluminum.
By using the disclosed material, more uniform and compact AAO holes can be formed on the surface of the material, so that the AAO holes are better combined with the injection molding material, and the air tightness between the top cover and the positive and negative electrode posts is improved.
Optionally, in step S4, the injection molding material used in the injection molding process is PPS or PBT.
PPS and PBT materials have smaller density, but higher strength, and have good fluidity in a molten state, so that the PPS and PBT materials have excellent processability, and can be well combined with AAO holes, so that the combination strength is improved, and the air tightness is further improved.
Optionally, in step S4, the conditions of the injection molding process are: the temperature of the front section is 290-360 ℃ and the temperature of the rear section is 330-360 ℃; the front stage pressure is 43-53kgf, and the rear stage pressure is 30-40kgf; the cooling time is 2-8s.
Under the injection molding condition, the injection molding material can be uniformly melted and flowed, and is better filled in AAO holes formed on the top cover and the positive and negative poles, and the top cover can be firmly combined with the positive and negative poles through proper extrusion pressure, so that the air tightness between the top cover and the positive and negative poles is improved.
In summary, the present application includes at least one of the following beneficial technical effects:
1. the application applies the micro corrosion of the acid corrosion inhibitor primary battery principle combined with anodic oxidation directional corrosion nanocrystallization treatment technology to the field of battery covers, firstly forms AAO honeycomb holes on the positive electrode area and the negative electrode area of the battery top cover and the positive electrode post and the negative electrode post, then uses an injection molding technology to respectively connect the positive electrode post and the negative electrode post with the AAO honeycomb holes on the positive electrode area and the negative electrode area by using injection molding materials as nanometer anchor nails, thereby tightly connecting the positive electrode post and the negative electrode post with the top cover, replacing the original sealing rings, and integrally connecting the positive electrode post and the negative electrode post with the top cover, thereby improving the connection stability and the sealing performance between the battery top cover and the electrode post, and further improving the safety performance of the battery.
2. The application applies AAO which is traditionally used for preparing nanowires by electrodeposition, preparing nano lattices by sputtering or MEB and preparing nano structures by sol-gel to a battery cover, and obtains excellent sealing effect and pressure-resistant effect.
Drawings
FIG. 1 is an SEM image of porous Anodized Aluminum (AAO) after cap nanocrystallization in example 1;
FIG. 2 is an EDS diagram of porous Anodized Aluminum (AAO) after cap nanocrystallization in example 1;
FIG. 3 is an enlarged view of a portion of a porous Anodic Aluminum Oxide (AAO) SEM of example 1 after nanocrystallization of the positive electrode column;
fig. 4 is an SEM image of the connection between the cap and the positive electrode post after filling PPS between the cap and the post in example 1.
Detailed Description
The present application will be described in further detail with reference to examples and comparative examples.
Example 1
Preparing an electrolysis Chi Huanshi agent: 100mL of an aqueous oxalic acid solution with a mass concentration of 10g/L and 2L of an aqueous phosphoric acid solution with a mass concentration of 50g/L were taken and mixed.
The top cover structure comprises a top cover, an anode post and a cathode post, wherein the top cover is 3 series aluminum, the anode post is 1 series aluminum, the cathode post is a copper-aluminum composite structure, copper is T2 copper, aluminum is 1 series aluminum, and laser welding is performed between the copper and the aluminum to form the copper-aluminum composite structure. The top cover is respectively provided with an anode region and a cathode region, the anode and cathode columns are connected with the anode region and the cathode region through a nano injection molding technology, and the nano injection molding technology comprises the following steps:
s1, pretreatment: the top cover, the positive electrode column and the negative electrode column are subjected to heat treatment firstly, and the heat treatment conditions are as follows: the top cover, the positive electrode column and the negative electrode column are placed in a muffle furnace, the temperature is raised to 450 ℃ at a heating rate of 5 ℃/min, and the mixture is kept stand for 2 hours. After cooling, alkali washing is carried out, and the cooled top cover and the anode and cathode columns are washed for 5min by using 1mol/L sodium hydroxide solution at 30 ℃. And then carrying out acid washing, and washing the top cover and the positive and negative electrode columns subjected to alkali washing with oxalic acid aqueous solution with the mass concentration of 20g/L for 2min at room temperature.
S2, nanocrystallization treatment of positive and negative electrode areas of the top cover: the top cover is used as an anode, the carbon rod is used as a cathode, the positive electrode area and the negative electrode area are used as the centers for positioning, the radius of the positive electrode area and the negative electrode area is 13mm, the temperature is 25 ℃, and the current carrying density of the anode is 0.5mA/m 2 The voltage of a feed back stabilized voltage source is 20V, the electrolytic electrochemical corrosion time is 2min, and the positive electrode area and the negative electrode area are directionally corroded in the electrolytic cell corrosion inhibitor;
s3, nanocrystallization treatment of the positive electrode column: the positive pole is used as an anode, the carbon rod is used as a cathode, the temperature is 25 ℃, and the current carrying density of the anode is 2.5mA/m 2 The voltage of the feed back stabilized source is 30V, the electrolytic electrochemical corrosion time is 2min, and the connection part of the positive pole and the positive pole area is directionally corroded in the electrolytic cell corrosion inhibitor. And (3) nanocrystallization treatment of a negative electrode column: the negative pole column is used as the anode, the carbon rod is used as the cathode, the temperature is 25 ℃, and the current carrying density of the anode is 1.5mA/m 2 The voltage of the feed back stabilized voltage source is 20V, the electrolytic electrochemical corrosion time is 2min, and the connection part of the negative pole column and the negative pole area is directionally corroded in the electrolytic cell corrosion inhibitor.
S4, filling gaps at the joints of the positive electrode column and the negative electrode column and the positive electrode region and the negative electrode region respectively through an injection molding process, wherein PPS is used as an injection molding material, the temperature of the front section is 330 ℃, and the temperature of the rear section is 340 ℃; the front stage pressure was 48kgf, and the rear stage pressure was 35kgf; the cooling time was 5s.
Example 2
Example 2 differs from example 1 in that the mass concentration of the oxalic acid aqueous solution is 8g/L and the volume is 120mL.
Example 3
Example 3 is different from example 1 in that the mass concentration of the phosphoric acid aqueous solution is 10g/L; in both step S2 and step S3, the conditions for the nanocrystallization are: the temperature was 35℃and the current density of the anode current was 2.5mA/m 2 The voltage of the feed back stabilized voltage source is 30V, and the electrolytic electrochemical corrosion time is 15min.
Example 4
Example 4 differs from example 1 in that the mass concentration of the phosphoric acid aqueous solution is 10g/L; in step S2 and stepIn S3, the nanocrystallization conditions are as follows: the temperature was 35℃and the current density of the anode current was 0.5mA/m 2 The voltage of the feedback stabilized source is 20V.
Example 5
Example 5 differs from example 2 in that the mass concentration of the phosphoric acid aqueous solution is 15g/L; in both step S2 and step S3, the conditions for the nanocrystallization are: the current density of the anode current is 1.5mA/m 2 The voltage of the feed back stabilized voltage source is 20V, and the electrolytic electrochemical corrosion time is 10min.
Example 6
Example 6 differs from example 1 in that the mass concentration of the phosphoric acid aqueous solution is 50g/L; in both step S2 and step S3, the conditions for the nanocrystallization are: the current density of the anode current is 5mA/m 2 The voltage of the feed back stabilized voltage source is 30V, and the electrolytic electrochemical corrosion time is 5min.
Example 7
Example 7 is different from example 1 in that, in step S1, the conditions of the heat treatment are: the top cover and the positive and negative electrode columns are placed in an environment where the temperature rises to 500 ℃ at a heating rate of 5 ℃/min, and are kept stand for 2.5h. After cooling, alkali washing is carried out, and the cooled top cover and the anode and cathode columns are washed for 2min by using 1mol/L sodium hydroxide solution at the temperature of 2 ℃. And then carrying out acid washing, and washing the top cover and the positive and negative electrode columns subjected to alkali washing by using an oxalic acid aqueous solution with the mass concentration of 20g/L for 5min at room temperature.
Example 8
Example 8 differs from example 1 in that the positive electrode post is 3 series aluminum, the negative electrode post is a copper-aluminum composite structure, copper is T2 copper, aluminum is 3 series aluminum, and friction welding is performed between copper and aluminum to form a copper-aluminum composite structure.
Example 9
Example 9 differs from example 1 in that in step S4, the injection molding material used in the injection molding process is PBT.
Example 10
Example 10 differs from example 1 in that in step S4, the conditions of the injection molding process are: the temperature of the front section is 360 ℃, and the temperature of the rear section is 360 ℃; the front stage pressure was 53kgf, and the rear stage pressure was 40kgf; the cooling time was 8s.
Comparative example 1
The cover plate of Yiwei 71173 common PPS injection molding is used, and the compression fluororubber sealing rings are used for sealing between the top cover and the positive and negative poles.
Comparative example 2
A simple cover plate of the Ningde age 71173 was used.
Comparative example 3
Comparative example 3 is different from example 1 in that the electrolytic Chi Huanshi agent is 2L of an aqueous oxalic acid solution having a mass concentration of 10 g/L.
Comparative example 4
Comparative example 4 differs from example 1 in that the agent for electrolysis Chi Huanshi is 2L of an aqueous phosphoric acid solution having a mass concentration of 50 g/L.
Comparative example 5
Comparative example 5 is different from example 1 in that the oxalic acid aqueous solution is 200mL.
Comparative example 6
Comparative example 6 is different from comparative example 1 in that, in both step S2 and step S3, the conditions of the nanocrystallization process are: the current density of the anode current is 6.5mA/m 2 The voltage of the feed back stabilized voltage source is 40V, and the electrolytic electrochemical corrosion time is 20min.
Comparative example 7
Comparative example 7 is different from example 1 in that the top cap and the positive and negative electrode columns are not heat treated in step S1.
Performance test data
The following performance tests were performed on the above examples and comparative examples:
(1) Drawing force detection
The method comprises the steps of welding a pole column (the melting width is more than or equal to 1.5mm and the melting depth is 0.5-1.6 mm) through penetrating laser welding by an aluminum row with the thickness of 2mm, fixing a top cover through a tool, fixing the aluminum row through a tensile machine, and testing the maximum force of the aluminum bar sheared from the pole column (perpendicular to the top cover direction) through a tensile testing machine.
(2) Rotation-stopping torsion detection
The method comprises the steps of welding a pole column (the melting width is more than or equal to 1.5mm and the melting depth is 0.5-1.6 mm) through penetrating laser welding by an aluminum row with the thickness of 2mm, fixing a top cover through a tool, fixing the aluminum row through a tensile machine, and testing the maximum force of the aluminum bar sheared from the pole column (parallel to the direction of the top cover) through a tensile testing machine.
(3) Helium test seal test
Fastening the top cover, connecting the air channel, sealing the measured part of the top cover with water, expelling air bubbles, opening a nitrogen valve of the steel cylinder, slowly pressurizing to 1MPa for 10 seconds, and observing whether air bubbles continuously emerge.
(4) Detection of aperture, hole spacing and hole depth of roof aluminum sheet by Scanning Electron Microscopy (SEM)
Table 1 table of performance test data
In example 1, SEM and EDS characterization were performed on top cover aluminum sheets obtained by nanocrystallization, see fig. 1 and fig. 2, and the EDS characterization results are: the components are mainly aluminum (Al) and oxygen (O), and the weight ratio of the aluminum (Al) to the oxygen (O) is Al:O= 58.95%:41.05% (wt%). SEM characterization is carried out on the positive pole obtained by nanocrystallization, and the SEM characterization is shown in figure 3. And after cutting the joint of the top cover and the positive pole, the nano injection molding condition of the metal surface is observed by using SEM characterization, and the drawing is shown in fig. 4.
As can be seen from the examples, comparative examples 1-2 and table 1, the cap structure disclosed by the present application is superior to the cap plate of comparative examples 1-2 in terms of the pulling force, the torsion resistance and the nitrogen test sealability of the cap obtained by the method disclosed by the present application. The reason is that the existing top cover structure uses a sealing ring to connect the top cover and the positive and negative electrode columns, and the sealing ring can fill the gap between the top cover and the positive and negative electrode columns, but still has the problem of insufficient air tightness, as can be seen from Table 1, the nitrogen test tightness of comparative example 1 is 15.0x10x (-8) ((Pa.m) 3 ) S, the seal of comparative example 2 is 10.0 x 10 (-8) ((Pa.m) 3 ) The S is much higher than the nitrogen test tightness of the examples of the present application, and the pulling force and the torsion-preventing force of comparative examples 1 and 2 are much smaller than those of the examples of the present applicationThe results of the measurement show that the top cover structure obtained by the application has excellent effects from the aspects of drawing force and torsion resistance and from the aspect of nitrogen gas tightness. Because the micro corrosion and anodic oxidation directional corrosion nanocrystallization technology combined with the principle of the acid corrosion inhibitor primary battery is applied to the field of battery covers, the injection molding material serves as a nano anchor to respectively connect the positive electrode column and the negative electrode column with the AAO honeycomb holes on the positive electrode region and the negative electrode region, so that the positive electrode column and the negative electrode column are tightly connected with the top cover, the original sealing ring is replaced, and the large-scale production can be performed, thereby reducing the cost. And this conclusion is also confirmed by SEM characterization of example 1, and it can be seen from fig. 1-4 that the top cap and the surface of the post both form a honeycomb structure, and that PPS fills the AAO honeycomb holes after injection molding to form a rivet-like composite structure. In summary, from any aspect, the top cover structure and the nano injection molding technology disclosed by the application have excellent effects when applied to the field of battery covers.
It can be seen from the combination of examples 1-2 and comparative examples 3-5 and Table 1 that the mass concentrations of oxalic acid aqueous solution and phosphoric acid aqueous solution in the electrolytic cell corrosion inhibitor and the ratio therebetween have a certain influence on the air tightness and the sustainable pressure of the finally formed integrated top cover. The electrolytic cell corrosion inhibitor mainly takes the phosphoric acid aqueous solution as a main component, the oxalic acid aqueous solution is added for mixing, the volume ratio of the added oxalic acid aqueous solution is not excessively high and is 5-6% of the volume of the phosphoric acid aqueous solution, and the effect obtained by mixing the phosphoric acid aqueous solution and the oxalic acid aqueous solution is better than that obtained by singly using any one of the phosphoric acid aqueous solution and the oxalic acid aqueous solution. The AAO holes obtained by using the mixed solution of oxalic acid aqueous solution and phosphoric acid aqueous solution as the electrolytic cell corrosion inhibitor have moderate pore diameters, and the distribution of the holes is more uniform, thereby being more beneficial to the combination with PPS.
In combination with examples 1, 3-6, comparative example 6 and Table 1, it can be seen that the process conditions during nanocrystallization have a certain influence on the tightness and the pressure that can be tolerated of the final integrated cap. The reason is that proper nanocrystallization treatment conditions are selected, AAO holes with moderate pore size and uniform arrangement can be formed, so that the AAO holes can be better combined with nano rivets formed by PPS, the connection between the positive electrode column and the negative electrode column and the top cover is firmer, the drawing force and the torsion resistance force can be borne, and meanwhile, the AAO holes also have better air tightness.
In combination with example 1, example 7, comparative example 7 and table 1, it can be seen that the pretreatment work before the nanocrystallization treatment is important and has an influence on the finally formed AAO pores. The reason is that the stress and internal lattice defects of the top cover, the positive electrode column material and the negative electrode column material can be removed in the pretreatment process, and meanwhile, pollutants on the surface can be removed, so that the surface is in more sufficient contact with the electrolytic cell solution, and further, a more uniform and compact AAO structure is formed, thereby being more beneficial to subsequent injection molding.
It can be seen from examples 1,8-10 and table 1 that the material of the cover plate, the material of the positive and negative electrode posts, the injection molding material and the injection molding process all have an influence on the air tightness of the top cover structure and the drawing force and the torsion resistance which can be borne. The reason is that under different materials and process conditions, the forms of the produced AAO holes are different, the injection molding process also affects the forms of the injection molding materials, and the combination states of the different AAO holes and the injection molding materials are different, so that the final combination effect is affected, and the selection of the materials of the cover plate, the anode and cathode columns, the injection molding materials and the injection molding process is also particularly important for the technical scheme disclosed by the application.
The above embodiments are not intended to limit the scope of the present application, so: all equivalent changes in structure, shape and principle of the application should be covered in the scope of protection of the application.
Claims (8)
1. A roof structure, its characterized in that: the nano injection molding technology comprises the following steps:
s1, pretreatment: the top cover, the positive pole and the negative pole are firstly subjected to heat treatment, and then are subjected to alkali washing and acid washing;
s2, nanocrystallization treatment of positive and negative electrode areas of the top cover: positioning by taking a top cover as an anode and a carbon rod as a cathode and taking an anode region and a cathode region as centers, and directionally corroding the anode region and the cathode region in the corrosion inhibitor of the electrolytic cell;
s3, nanocrystallization treatment of positive and negative electrode columns: respectively taking the positive and negative poles as anodes and taking a carbon rod as a cathode, and directionally corroding the parts of the positive and negative poles, which are connected with the positive and negative pole areas, in the corrosion inhibitor of the electrolytic cell;
s4, filling gaps at the joints of the positive electrode column and the negative electrode column and the positive electrode region and the negative electrode region respectively through an injection molding process;
the electrolyte Chi Huanshi agent is formed by mixing an oxalic acid aqueous solution and a phosphoric acid aqueous solution, wherein the mass concentration of the oxalic acid aqueous solution is 8-10g/L, the mass concentration of the phosphoric acid aqueous solution is 10-50g/L, and the volume ratio of the oxalic acid aqueous solution to the phosphoric acid aqueous solution is (5-6): 100;
in step S2 and step S3, the conditions of the nanocrystallization process are: the temperature is 25-35 ℃, and the current carrying density of the anode is 0.5-5mA/m 2 The voltage of the feed back stabilized voltage source is 20-30V, and the electrolytic electrochemical corrosion time is 2-15min.
2. A roof structure according to claim 1, wherein: in step S1, the conditions of the heat treatment are: placing the top cover and the positive and negative electrode columns in an environment with the temperature rising rate of 5 ℃/min to 450-500 ℃, and standing for 1.5-2.5h.
3. A roof structure according to claim 1, wherein: in step S1, the conditions for alkaline washing are: washing the heat treated top cover and the positive and negative poles with sodium hydroxide solution of molar concentration 1mol/L at 25-30deg.C for 2-8min.
4. A roof structure according to claim 1, wherein: in step S1, the conditions for pickling are: washing the top cover and the anode and cathode columns after alkali washing with oxalic acid water solution with the mass concentration of 20g/L for 2-5min at room temperature.
5. A roof structure according to claim 1, wherein: in step S2, the radius of the positive and negative electrode areas of the directional etched top cover is 13-14mm.
6. A roof structure according to any one of claims 1-4, wherein: the top cover is 3 series aluminum; the positive pole is 1 series aluminum or 3 series aluminum; the negative pole post is copper aluminum composite structure, copper is T2 copper in the copper aluminum composite structure, and aluminum is 1 series aluminum or 3 series aluminum.
7. A roof structure according to any one of claims 1-4, wherein: in step S4, the injection molding material used in the injection molding process is PPS or PBT.
8. A roof structure according to claim 1, wherein in step S4, the injection molding process is performed under the following conditions: the temperature of the front section is 290-360 ℃ and the temperature of the rear section is 330-360 ℃; the front stage pressure is 43-53kgf, and the rear stage pressure is 30-40kgf; the cooling time is 2-8s.
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| CN107815691A (en) * | 2017-12-20 | 2018-03-20 | 苏州德菱化学品有限公司 | A kind of aluminium workpiece surface nano aperture processing method for nanometer injection |
| CN209183583U (en) * | 2018-11-22 | 2019-07-30 | 芜湖天弋能源科技有限公司 | Top cover structure of power battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107815691A (en) * | 2017-12-20 | 2018-03-20 | 苏州德菱化学品有限公司 | A kind of aluminium workpiece surface nano aperture processing method for nanometer injection |
| CN209183583U (en) * | 2018-11-22 | 2019-07-30 | 芜湖天弋能源科技有限公司 | Top cover structure of power battery |
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